Acylheterocyclic derivatives of urea suitable for use as agricultural antiparasitics

ABSTRACT

The invention describes urea derivatives and process for their preparation which are useful as agricultural antiparasitic agents, herbicides and growth regulators and which have the general formula IN WHICH R represents a 5- or 6-membered heterocyclic radical containing one or two identical or different hetero atoms; R&#39;&#39; represents hydrogen, a methyl radical or a CH2CH2CN-radical; R&#39;&#39;&#39;&#39; represents one of the following radicals: an optionally saturated alkyl radical containing from one to four carbon atoms, a lower alkoxy radical, a lower alkoxy lower-alkyl radical or a CH2CH2CNradical; A represents one or two identical or different radicals selected from the following: halogen, NO2, lower alkyl, lower alkoxy, CH3, SCN.

United States Patent Poignant et al.

is] 3,681,389 (451 Aug. 1, 1972 [54] ACYLHETEROCYCLIC DERIVATIVES OF UREA SUITABLE FOR USE AS AGRICULTURAL ANTIPARASITICS [72] Inventors: Pierre Poignant; Daniel Pillon, both of Lyon; Rodolphe Caffiero,

- Francheville-le-Bas, all of France [73] Assignee: PEPRO-Societe Pour le Developpement et La Vente de Specialites Chimiques [22] Filed: March 31, 1970 [21] Appl.No.: 24,358

Related US. Application Data [62] Division of Ser. No, 705,292, Feb. 14, 1968,

Pat. No. 3,542,797.

[30] Foreign Application Priority Data Feb. 16, 1967 France ..48303 [52] US. Cl. ..260/332.2 C [51] Int. Cl. ..C07d 63/12 [58] Field of Search.....260/332.2 C, 553 E, 332.2 R; 71/90 [56] References Cited UNITED STATES PATENTS 3,498,780 3/1970 Soper et al ..7l/9O FORElGN PATENTS OR APPLICATIONS 1,392,499 2/1965 France ..7l/9O Primary Examiner-Henry R. .liles Assistant Examiner-Cecilia M. Shurko AttorneyBrowdy and Neimark [57] ABSTRACT The invention describes urea derivatives and process for their preparation which are useful as agricultural antiparasitic agents, herbicides and growth regulators and which have the general formula A I O R" 7 Claims, No Drawings ACYLIIETEROCYCLIC DERIVATIVES OF UREA SUITABLE FOR USE AS AGRICULTURAL ANTIPARASITICS This application is a division of co-pending application Ser. No. 705,292 filed Feb. 14, 1968 now US. Pat. No. 3,542,797 patented Nov. 24, 1970.

This invention relates to new chemical compounds derived from urea, to a process for their preparation and to their use as agricultural antiparasitic agents and, in particular, as herbicides and growth regulators.

The ureas according to the invention correspond to the general formula in which R represents a 5- or 6-membered heterocyclic radical containing one or two identical or different hetero atoms; R represents hydrogen, a methyl radical or a CH CH CNradical; R" represents one of the following radicals: an optionally saturated alkyl radical containing from one to four carbon atoms, a lower-a1- koxy radical, a lower-alkoxy lower-alkyl radical or a CH CH CN-radical; A represents one or two identical or different radicals selected from the following: halogen, N0 lower alkyl, lower alkoxy, CP SCN.

These compounds are prepared by condensing a dior tri-substituted urea with a heterocyclic acid chloride. The dior tri-substituted urea used as starting material is prepared by known methods such as condensing phosgene with an aniline and then reacting a primary or secondary amine with the chlorocarbonate formed, or reacting the same amines with an arylisocyanate, or reacting a suitably substituted urea with an aniline.

Condensation of the dior tri-substituted urea with a heterocyclic acid chloride takes place in accordance with the following equation:

This reaction may be carried out in any organic solvent such as benzene in the presence of a suitable halogenated hydracid acceptor such as pyridine.

In one preferred embodiment of this process, pyridine itself is used as solvent for the reaction mixture, being employed in a large excess relative to the theoretical quantity. This reaction is readily carried out at room temperature and may be accelerated by heating to such an extent as to bring the reaction mixture up to a temperature of around 110 C. In general, less intense heating (i.e. from 40 to 70 C) will be sufiicient because symmetrical N,N'-diaryl ureas can be formed at higher temperatures in dependence upon the heterocyclic acid chlorides used.

In cases where the heterocycle contains nitrogen as hetero atom, the acid chloride used will be in hydrochloride form which is the most readily accessible.

The reaction mixture may be treated in three ways:

1. It may either be poured into an excess of chilled, diluted HCl. The excess pyridine is eliminated in the form of pyridine hydrochloride which is soluble in water. The trior tetra-substituted urea is precipitated. This precipitation often assumes an oily form, solidification beginning after only a few hours. A fine crystalline solid can be more rapidly obtained by adding to the reaction mixture 10 percent of its own weight of alcohol before decomposition.

2. Most of the excess pyridine may be distilled off in vacuo (20 to mm. of mercury) at a temperature below 50 C. The gummy residue is then stirred with ice water. The rest of the pyridine in excess together with the pyridine hydrochloride formed during condensation is rendered soluble in water, the urea being precipitated.

3. The reaction mixture may be directly poured into water with preliminary recovery of the pyridine. This alternative is applied in the particular case of heterocyclic acids containing a nitrogen atom in order to avoid the formation of a hydrochloride of trior tetrasubstituted urea. On the other hand, the urea is precipitated in a well crystallized form under these conditions.

EXAMPLE 1 19.85 g (0.1 mol) of N-4-chlorophenyl-N,N'- dimethyl urea are dissolved in cc. of pyridine. 17.8 g (0.1 mol) of the hydrochloride of isonicotinic acid chloride are added to the resulting solution. This hydrochloride is in the form of a powder which is fed into the flask by means of an archimedian screw in a stream of nitrogen. A precipitate of pyridine hydrochloride is then formed in large quantities. The reaction product is left standing for 24 hours and then poured slowly in ice water with vigorous stirring. A very fine precipitate is formed, being separated by filtration, washed with ice water and then dried in vacuo. N-4-chlorophenyl-N-isonicotinyl-N,N'-dimethyl urea is obtained in a yield of 21.8 g of 71.8 percent, M.p. 161 C The results of analysis are as follows;

c H N Calculated: 59.30 4.61 13.83 Found: 59.63 4.76 13.85

The product obtained is soluble in a dilute acid medium by virtue of the hydrochloride formed. Generally speaking, each time the heterocycle contains a nitrogen hetero atom, the urea obtained may be used in a quaternized form obtained by the action of compounds such as acids (hydrochloric acid, alkyl or arylsulphonic acid and so on), alkyl halides and so on, on the urea.

Thus, by treating the compound of Example 1 with a solutionof hydrochloric acid, the hydrochloride of the urea (M.p. 152 C) readily soluble in water is obtained in a yield of 98.5 percent.

EXAMPLES 2 to 6 The following products are obtained by applying the procedure described in Example 1:

No. R R" R A Yield M.p.

2 CH CH 4-pyridyl 3,4-dichloro 69.3% 1 17-1 l8 3 CH CH S-pyridyl 3,4-dichloro 93.9% 124C 4 CH CH J-pyridyl i-chloro 86. l% 104-105C 5 CH CH S-pyridyl H 68.3% 121C 6 CH: CH, 4-pyridyl 4-CH O 30.9% 125C 7 CH CH 4-pyridyl 3-CF 64.1% 1 l6-l 18C EXAMPLE 8 EXAMPLES 9 to 13 The following compounds are prepared by applying the procedure described in Example 8:

The compounds according to the invention show remarkable antiparasitic properties enabling them to resolve a large number of problems that are encountered in the agricultural field.

It is possible in dependence upon the nature of the radicals A, R, R and R" and upon the doses and conditions of use to obtain products that are either growth regulators, i.e., products capable of influencing the normal development of the plants to which they are applied. Thus, they are able in particular to shorten the stems of cereal crops enabling the socalled beating-down phenomenon to be avoided, or to produce defoliation or to thin out or, in contrast, to multiply flowers or fruit and so on,

or herbicides whose activity is total and which destroy weeds, undergrowth, shrubs and so on,

or herbicides whose activity is selective which enables them to be used to destroy all the casual weeds capable of inhibiting the development of the plants which it is desired to protect.

The herbicidal activity of the compounds according to the invention is also governed by the conditions of use. Some of them develop their maximum activity (or selectivity) in cases where treatment is carried out be fore seeding or planting, some are essentially suited to pre-emergence treatment (after seeding and before sprouting either of the plants or of the weeds), whilst others are best suited to post-emergence treatment of the plants and/or weeds.

It will therefore be possible for the user to find among the range of products according to the invention products which will enable him most effectively to resolve the problem by which he is confronted.

The following examples demonstrate some aspects of the activity of the compounds according to the invention. The sole object of these examples is to illustrate the present description without in any way limiting its scope to the applications mentioned therein. Naturally,

the invention covers all the antiparasitic applications of the compounds of formula (1) irrespective of the doses in which and the conditions under which they are used.

EXAMPLE 14 A wettable powder ready for use is prepared by adding 20 parts of active material to a mixture containing 74 parts of an inert filler (Argirec B 22), 5 parts of a deflocculant (Argrinol C 14) and 1 part of a wetting agent (Erganol AT 30).

The wettable powder thus obtained is diluted to the required concentration just before it is applied in dependence upon the quantity of active material which it is desired to apply per hectare.

EXAMPLE 15 When used in a dose of 8 kg/ha. in pre-emergence treatment, product No. 9 completely .destroys such grasses as blackgrass (Alopecurus myosuroides), ryegrass (Lolium italicum), panic grass (Echinochloa crusgalli), millet (Panicum miliaceum), barley (Hordeum distichum) and such dicotyledones as carots (Daucus carota), Haricot beans (Phaseolus vulgaris), flax (Linum usitatissiumum), turnips (Brassica napus), buckwheat (Polygonum fagopyrum), tomatoes (Solarium esculentium) and peas (Pisum sativum). When applied in the same close, product No. 12 is also phytotoxic on most of the test plants, both monoand cli-cotyledones.

By contrast, the same product, when applied in a dose of lkg/ha, is completely selective on maize (Zea mays), barley and oats (Avena saliva), completely destroying casual weeds such as millet, panic grass and rye grass.

EXAMPLE 16 When applied in a dose of 8 kg/ha, product No. 13 is selective on Haricot beans and completely destroys millet, turnips, buckwheat, tomatoes and tumsole (Helianthus annus).

When applied in an equivalent dose of 8 kg/ha, product No. l is completely selective on wheat (Triticum vulgan's), Haricot beans, soya beans and cotton, and completely destroys oats, millet, rye grass, blackgrass, carots, turnips, buckwheat, tomatoes and turnsole.

EXAMPLE 1? When applied in a dose of 4 kglha, product No. 3 is selective on corn, barley, oats and Haricot beans and completely destroys such grasses as millet, panic grass and rye grass, and dicotyledones such as carots, turnips, buckwheat, tomatoes and turnsole.

EXAMPLE 18 turnsole. It is 80 percent effective on Haricot beans and tomatoes.

EXAMPLE 19 A solution (containing 0.5 kg/ha.) of the compound of Example 1 (used in the form of its hydrochloride) is sprayed on to young corn seedlings 1 week old.

Samples taken 4 weeks after the treatment show a reduction in height of 30 percent in the treated corn relative to control plants.

Despite this reduction in height, the corn treated does not show any signs of weakness, its density per square meter being equal to that of control plants.

These few examples demonstrate very clearly the remarkable polyvalent action of the products according to the invention.

The products according to the invention may be used on their own, although generally they will be converted into a more practical form of use for application.

The type of formulation selected will be governed by the physico-chemical properties of the products and by the type of application for which it is intended to use them. Thus, depending on circumstances, the product will be used in the form of spraying powders, solutions in mineral or organic solvents, direct or inverse emulsions, suspensions, granules and so on, containing in addition to the active material fillers and various additives such as wetting agents, emulsifiers, dispersants, adhesives, deflocculants, anti-clumping agents and so on, such as those described in Frears work Chemistry of Insecticides, Fungicides and Herbicides 2nd Edition, pp. 277-291.

What is claimed is:

1. A compound selected from the group having the general formula:

in which R represents a S-membered heterocyclic radical containing at least one hetero atom selected from the group consisting of thienyl and fury];

R represents hydrogen or a methyl radical;

R" represents an alkyl radical containing from 1-4 carbon atoms, a lower-alkoxy radical, or a loweralkoxy lower-alkyl radical; and

A is selected from the group consisting of hydrogen,

N0 lower alkyl, lower-alkoxy, CE, and SCN radicals and may include one or two identical or different radicals.

2. A compound as claimed in claim 1 wherein A is 4- chloro, R is methyl, R" is methyl and R is thienyl.

3. A compound as claimed in claim 1 wherein A is chloro, R is methyl, R is methyl and R is furyl.

5. A compound as claimed in claim 1 wherein A is hydrogen, R is methyl, R" is methyl and R is furyl.

6. A compound as claimed in claim 1 wherein A is 3,4-dichloro, R is methyl, R" is methyl and R is thienyl.

7. A compound as claimed in claim 1 wherein A is hydrogen, R is methyl, R is methyl and R is thienyl. 

2. A compound as claimed in claim 1 wherein A is 4-chloro, R'' is methyl, R'''' is methyl and R is thienyl.
 3. A compound as claimed in claim 1 wherein A is 3,4-dichloro, R'' is methyl, R'''' is methyl and R is furyl.
 4. A compound as claimed in claim 1 wherein A is 4-chloro, R'' is methyl, R'''' is methyl and R is furyl.
 5. A compound as claimed in claim 1 wherein A is hydrogen, R'' is methyl, R'''' is methyl and R is furyl.
 6. A compound as claimed in claim 1 wherein A is 3,4-dichloro, R'' is methyl, R'''' is methyl and R is thienyl.
 7. A compound as claimed in claim 1 wherein A is hydrogen, R'' is methyl, R'''' is methyl and R is thienyl. 